New azo dyestuffs and process of making same



' may be again diaz otized and Patented June 16, 1931.

I- E S ATES PATENT? oFFicE;

snons KALISOHER, or FRANKFORT-ON-THEMAIN, Annnrcrmnn FLEISCHHAUER, on: FRANKFORT-ON-THE-MAIN-FEGHENHEIM, GERMANY, ASSIGNORS. 'ro GENERAL ANIIJINE.WORKS, INQ, OF NEW YORK, N. Y., A. CORPORATION 01 DELAWARE NEW Azo DYESTUFIES AND rnocnss on AKING SAME No Drawing. Application filed August 22, 1929, Serial No.:387,802, and in Germany'August 28, 1928.

Our present invention relates to new azodyestuffs and tea process of preparing the same. I

We have found that new very valuableazodyestuifs are obtained 'by diazotizing 4- amino-diaryl-cyclohexane-d-oxamic acids, obtainable, for instance,- acc0rding to the process disclosed inour copending application Ser. N 0. 387,798, filed August22, 1929, and, combining the diazo-c'ompounds with azo-components. These dyestufisyield on saponification new valuable dyestuffs :which Combined with azo-components. I

Our new dyestufis correspond to the general formula: I

tain further 'azoegroups.

They are distinguished by clear shades: and excellent properties of fastness especially to milling and light. They" are mainly suitable for dyeing animal fibers,obut according to the azo component's appliedv they Emay par:

tially be used alsofor dyeing cotton or viscose silk. When az'o-components containing chromablegroups are applied, valuable chromable dyestuffs of an excellent fastness are produced.

In order to further illustrate our inVen-,

tion the following examples'are given, the partsbeing by Weight and all temperatures 111 centigradedegrees. But we wish to :be

understood that we are not limited to the par ticular conditions nor to the specific products;

mentioned therein.

Example 1 33.5 parts of 4-amino-3.3-dichlor0-diphenyl-l.17-cycl0heXane-4-0Xamic acid are dissolved inlOOparts ofwarm water with the addition of the sufficient amount of am monia. To this solution a concentrated aqueoussolution of 6.9 parts of sodiumnitrite and;

then 52 parts of hydrochloric acid (specific gravity=1.l6) are added while cooling. The

diazo-compound precipitates partially. In

order to finish the reaction the mass is stirred for a short time. Then it is allowed torunr,

slowly into a solution containing 26 parts of the sodium salt of Q-jhydroXy-naphthalene-6 sulfonic acid and an excess of soda. The formation of the dyestutf I is finished after a short time. Thenew dyestufi is isolated by 1 the addition of common salt, then, filteredand dried. It corresponds to the formula:

A similar dyestuff is obtained by'starting from 4-amino-3.3-dibrom0-1.1'-diphenylcyclohexanee oxamic acid.

, p 7 Ho- 2 Nn o o-ooon v 7 v SO3H Example 2 39.8 parts of -amino-EBB-dimethoXy-diphenyl-1.1 cycloheXane-eV-oxamic acid are diazotized as described in Example 1 and the diazo-compouud is introduced into a solution of soda and 42.5 parts of l-benzoylamino-8-hydroXy-naphthalene-MSdisulfonic acid. When after a short time the formation of the dyestufi is finished, the dyestuff is isolated as described in the foregoing example. It corresponds to the formula:

' OCH;

Qmrooooon on It represents when dry a violetish brown powder easily soluble in water, dyeing wool fast clear reddish violet shades.

Dyestuffs of likewise clear, somewhat more yellowish shades are obtained by replacing the diazo-compound by that of sl-amino-3.3'- dimethyl-diphenyl-cyclohexane l oxamic acid or of l-amino-3.3-dimethyl-diphenyl- 4:" -1nethyl-cycloheXane-et-oxamic acid.

These diaZo-compounds yield when combined with l-benzoylamino S-hydroxynaphthalene-3.6-disulfonic acid or l-toluene-sulfamino-8-hydroxy-naphthalene-3.G-disulfonic acid or other acylamino-naphthol-sulfonic acids, new azodyestuffs which dye wool bright red to violet shades of the same good fastness.

Dyestuffs of the same properties are obtained by starting from 4:-a1nino-3.8-diethoxy-diphenyl-cyclohexane-lf-oxamic instead of the corresponding dimethoxy compound mentioned above.

Emample 3 36.6 parts of l-amino-3.3-dimethyl-diphenyl-cyclohexane--0xamic acid are diazotized as described in Example 1 and the diazo-compound is combined with a solution containing soda and the sodium salt of 2.8-dihydroxy-naphthalene-6-sulfonic acid. The

dyestuff thus obtained corresponds probably to the formula produced dyeing somewhat more clear yellowish shades.

The first named dyestuif may be saponified for instance by boiling it in a caustic soda solution of about 5% strength. The saponh fication product corresponds to the formula:

OH NH-CO-O It represents a dark red powder, easily soluble in water, yieldingon wool fast bluish red dyeings which are somewhat more bluish than those of the original dyestuif.

I Example 4 It is easily soluble in Water and dyes wool fast clear yellow shades.

Thepaste of this dyestuff is heated with 400 parts 01 a caustic soda solution of about strength. The dyestluff thus saponified is precipitated by the addition of common salt, filtered and made to a paste by means of water. To this paste an aqueous solution SOaH of 6.9 parts of sodium nitrite and then 46.5 parts of hydrochloric acid of v the specific gravity 1.16 are added while stirring at 0'5. Afier about one hours standing the suspension is allowed to run into a solution of soda and 47'parts' of the dyestufl 1-amino-2- (4nitrophenylazo) -8,-hydroxy naphthalene 3.6- disulfonic acid- After stirring fortsome hours a green solution is obtained. The dyestufi is isolated by the addition of hydrochloric acid and common salt. 7 It corre-- sponds tothe formula:

. oH NH, 2 2

It represents a greygreen powder, easilysoluble in warm water, producing clear yellowish green dyeings of a very good fastness.

lution of 22.3 parts of the sodium salt of:

Example 5 36.6 parts of 4-amino-3.3' dimethyl-di-V phenyl-cyclohexaneV-oxamic acid are diazotized according to Example 1. The diazocompound is allowed to run slowly into a socooling With ice. The mass is stirred at O 5 for 1 hour and'introduced into a-solution of soda and 30 parts ofthe sodium salt of 1@henylamino-naphthalene 8 sulfonic acid. After a-short time the mass is warmed to about 60 and thedyestuff is isolated inthe usual manner. It corresponds to the for Omaeco ooon It represents a black 'powderzdyeing Tw'ool black shades of an excellent fastness to washing and milling.

When saponified this dyestufi yields a new' dyestuif dyeing somewhat more bluish shades.

In a similar manner bluish black, grey or brown dyestuffs can be'produced according to the components applied.

Byusing as end-component 2- l aminophenyl amino) 5 hydroxy naphthalene-7 sulfonic acid a dyestuff is obtained yielding on cotton Violet dyeings which may be diazotized and developed with 2-naphth0l turning thereby to blue.

Example 6 The diazo-compound-of 36.6 parts of 4- amino-3;3-dimethyl diphenyl-cyclohexanet'-OX3.I[1lC acid, prepared according to Example 1, is introduced into a solution of soda and 47 parts of 1-amino,-2 (tnitro-phenylazo) -8-l1ydroXy-naphthalene- 3.6 disulfonicacid. When after about 3 hours the combination is complete, the dyestufi is isolated by the addition of common salt. It corresponds to the formula:

It represents a dark powder, easily soluble in water, dyeing greenish blue-black shades.

Example 7' l I I The diazo-compound of '36. 6 parts of 4;- amino-3.3 -dimethyl diphenyl cyclohexane- 4-oxa1nic acid, prepared according to Examsoar i I ple'1,is:introduced at 510 into a solution of 14 parts of salicylic acid and 50 parts of a caustic soda 1 e of 40 B. in 300: parts of water. The ormed dyestufi is isolatedfiin the customary manner and saponified and re d iazotized according to Example 3. The suspension of the diazo-compoundxthus obtained is allowed to run at 510 into a solution of soda and 29 parts of 1- (Q-chloro-5- sulfo phenyl) 3 methyl- 5 -pyrazolone. In this manner a clear yellow dyestufi' is produced corresponding to the formula:

$113 ()OOH H: H: I N=N- OH H CH3 C==N SOzH It iseasily soluble in water and dyes wool 'fast yellowish shades scarcely changed by afterchroming but improved thereby as to their fastness.

When the pyrazolone compound is replaced by the equivalent amount of 1-amino-2-(4- nitro-phenyl azo) -8 hydroxy naphthalene- 3.6-disulfonic acid, a dyestufi is obtained which dyes the animal fiber greenish blue shades becoming fast bright yellowish green when after-chromed.

' By using Q-amino-S-hydroXy-naphtha-lene- 6-sulfonic acid as second component a brown chromable dyestufi of a very good fastness is produced.

Salicylic acid may also be replaced byother components having chromable groups in order to produce other chromable dyestuffs.

We claim: I

1. A process which comprises diazotizing a -amino-diaryl-cycloheXane-l-oxamici acid of the general formula:

wherein one X means hydrogen or methyl,

the other Xs hydrogen and the Ys mean azocomponent.

2. A process which comprises diazotizing a 4-amino-diaryl-cyclohexane-4t-oxamic acid of the general formula H: H: i

| NH.CO.COOH V X11 x11 wherein one X means hydrogen or methyl, the other Xs hydrogen and the Y s mean hydrogen, halogen, methyl or alkoXy-groups, combining the diazocompound with any azocomponent. a

4. As new compounds the azo-dyestufis of the general formula:

wherein one X means hydrogen or methyl,

, the other Xs hydrogen, the Ys mean hydrogen, halogen, methyl or alkoxy-groups, Z means NI-I or NH-CO-COOH and the azo-component may contain further azogroups, which compounds are colored powders, soluble in water, yielding dyeings of an excellent fastness.

5, As new compounds the azodyestuffs of the general'formula:

NH.GO.COOE. H x11 Y wherein one X means hydrogen or a methylgroup, the other Xs hydrogen, the Ys stand for hydrogen, halogen, methyl or-alkoxygroups, A is hydrogen, OH, NIL, Oacyl, NH-acyl, or N=Nazo-component, B hydrogen or N=N-aryl and 'n is the number 1 or 2, which compounds are colored powthe diazocompound with any azo BIZ ders, soluble in water, yielding dyeings of an excellent fastness.

6; As new compounds the azodyestulfs of the general formula:

wherein the Ys stand for hydrogen, halogen, methyl or alkoxy-groups, A is 0H,? NH Oacyl, NHeacyl and 12, means the number 1 or 2, which compounds are colored powders, soluble in water, yielding dyeings of an excellent fastness.

7. As a new Compound the azo-dyestufi of y the probable formula:

1 1 \QNH-OO-JJOOH v which compound represents when dry 2. dark red powder, easily soluble in water, dyeing e animal fibers clear bluish red shades of an excellent fastness.

In testimony whereof,,we aflix our signatures. 7

GEORG KALISCHER. RICHARD 'FLEISCHHAUER; 

